Perchloryl aromatic compounds



This invention relates to a novel class of derivatives of perchlorylfluoride and to a process for their preparation. More specifically itpertains to perchlorylaromratic compounds.

Perchloryl fluoride, ClO F, whose structural formula is is asurprisingly stable fluorine derivative of perchloric acid. (H. Bode andE. Klesper, Zeitschrift fur anorganische und allgemeine Chemie, 255, 275(1951) and A. Engelbrecht and E. Atzwanger, Monatshefte fiir Chemie, 83,1087 (1952).) Its chemical reactivity with organic compounds haspreviously been unknown.

We have now discovered a series of novel aromatic compounds derived bythe reaction of perchloryl fluoride with certain aromatic compounds. Wehave found that the fluorine atom of perchloryl fluoride can be replacedwith a substituted or unsubstituted aryl radical to form a primary classof hitherto unknown compounds identified as perchlorylaromaticcompounds.

We have further found that substituents can be in troduced into the arylradical of our primary perchloryla imatic compounds to form, as asecondary class, a wide variety of derivatives of our primaryperchlorylaromatic compounds. Furthermore We have found that a compoundof our secondary class of perchlorylaromatic compounds can be reacted toform other compounds of the primary class, thus providing an alternativeroute to certain of these compounds. By a series of reactions, includingreaction with perchloryl fluoride at an appropriate stage, a wide rangeof perchlorylaromatic compounds can thus be produced, embracingessentially the entire field of aromatic chemistry. As the result of ourdiscovery, therefore, a new organic unit process, perchlorylation, maynow take its place alongside nitration, sulfonation, diazotization,etc., in the synthesis of new aromatic compounds.

The compounds of our invention have the formula wherein AI is asubstituted or unsubstituted aromatic radical.

The group Ar may represent the substituted or unsubstituted aromaticradical derived from an aromatic compound which is directly capable ofentering into a chemi- 3,l4 2,74 Patented July 28, 1964 cal reactionwith perchloryl fluoride, e.g., benzene or chlorobenzene. Ar may alsorepresent a substituted aromatic radical which can be derived by thechemical reaction of another reactant, e.g., HNO with the aromaticradical of a primary perchlorylaryl compound. Furthermore, Ar mayrepresent the substituted or unsubstituted aromatic radical which can bederived by any number of chemical reactions with the substituted orunsubstituted aromatic radical of a primary or secondaryperchlorylaromatic compound. Because of the wide variety of compoundswhich can be derived by treating a reactant compound chosen from eitherour primary or secondary perchlorylaromatic compounds with anotherreactant com pound according to conventional procedures of aliphatic oraromatic chemical synthesis, it is possible, of course, for many of ourperchlorylaromatic compounds to be derived by several chemical routes.For example, 3,4- dichloroperchlorylbenzene can be derived either byreacting 2,3-dichlorobenzene with erchloryl fluoride or by reacting4-chlorobenzene with perchloryl fluoride and chlorinating the4-chloroperch1orylbenzene formed to 3,4- dichloroperchlorylbenzene. Byway of further example, perchlorylbenzene can be made by perchlorylationof benzene, or by deamination of 3aminoperchlorylbenzene.

Examples of said aromatic radical ,Ar, when unsubstituted, are phenyl,biphenylyl, alpha-naphthyl, betanapthyl, alpha-anthryl, beta-anthryl,gamma-anthryl, phenanthryl, naphthacyl, chrysyl, pyryl, and triphenylyl.The aromatic radical Ar, when substituted, may contain from 1 to 5nuclear substituents. Examples of said substituents are R, where R isalkyl with 1 to 12 carbon atoms, including methyl, ethyl, propyl, butyl,pentyl, hexyl, octyl, nonyl, and dodecyl, including all isomeric formsof the latter seven and the halogenated, oxygenated, esterified,condensed, nitrated, sulfonated, cyanated, aminated, and closed-ringforms of all said alkyls; T, where T is halogen, including bromine,chlorine, fluorine and iodine, phenyl, and nitrophenyl; and Q where Qrepresents hydroxy; amino; nitro; cyano, thiophenyl; sulfhydryl and SRwhere R is the same as defined above; sulfo; %O X, where X is halogen asdefined above, sulfinyl; sulfonyl; sulfino; halosulfinyl; halosulfonyl;amidosulfinyl; amidosulfonyl; carbamyl;

SOOR

where R is the same as defined above; perchlorylaryl; carboxy; nitroso;azo; azoxy; hydrazo; carbalkoxy;

NHCOR where R is as defined above; NHCOC H OR where R is as definedabove; phenoxy; N NX where X is halogen as defined above; N(N)X, where Xis halogen as defined above; COY where Y is halogen as defined above,hydroxy, OM, where M is sodium, potassium or lithium, phenoxy, R asdefined above, amino, phenyl, hydrogen, or OR where R is as definedabove; and a radical derived from a heterocyclic compound including theradicals of furan, thiophene, pyrrole, indole, pyridine, piperidine andquinoline; aryl radical, including phenyl, biphenylyl, napthyl,u-anthryl, ,B-anthryl, v-anthryl, phenanthryl, naphthacenyl, chrysenyl,pyrenyl and sition on the benzene ring, there can be a Q in thenumtriphenylyl, and said aryl radical having R, T and Q subher 3position, or two Qs in the 2 and 5 positions, etc. stituents. Similarly,if there are two Rs and/ or TS in the 2 and Our primaryperchlorylaromatic compounds comprise 5 position, there can be a Q inthe number 3 position, those in which Ar is phenyl or substitutedphenyl, for 5 etc. example, perchlorylaromatic compounds having theformula 934110 b iQ Th 50 The interrelations of our perchlorylaromaticcompounds are substantially as shown in the following chart:

and Q indicate the position of the substituent indicated at the head ofeach column with respect to the perchloryl fluoride radical, and thenumerals under a and b and 0 indicate the number of substituents,essentially as shown. For example, if there is an R or T in the number 4po- In introducing the first Q group into a primary perchlorylaromaticcompound where at least one R or T group is present, the R and/or Tgroup or groups and the perchloryl radical already present influence theposition which will be occupied by the Q. In introducing a second or aplurality of additional Q groups, the particular group or groups whichcan be introduced in the presence of the already present perchloryl, R,T, and Q groups will be influenced, as will the ease of substitution ofsaid new Q group or groups, by the said already present groups. In orderto introduce the new Q groups it is necessary, in certain cases, toalter the character of one or more of the already present Q groups inorder to permit the new Q group or groups to enter. For example, in thecompound -NO2, where NO2 is a Q group, in order to introduce a new -NOgroup into the ring, for example in the 6 position, it is necessary toconvert the NO group present in the 3 position to a halide, for example,by reduction, diazot lation and halogenation before introducing the newNO group.

As shown by the definition of Q, more than one perchloryl group can bepresent in the molecule of the perchlorylaromatic compound. Theadditional perchloryl radical or radicals may be introduced by couplingtwo or more molecules of a perchlorylaromatic compound.

Examples of our preferred compounds are shown in Table I.

TABLE I Perchlorylbenzene 3 -iodoperchlorylbenzenev3-sulfamidoperchlorylbenzene -;3-cyanoperchlorylbenzeneB-carboxyperchlorylbenzene .3-phenoxyperchlorylbenzene4-chloromethylperch1orylbenzene 4-hydroxymethylperchlorylbenzene4-dichloromethylperchlorylbenzene t4-trichloromethylperchlorylbenzene:l4-trifluoromethylperchlorylbenzene 4-carboxyperchlorylbenzene4-fluoroperchorylbenzene 2,S-dimethylperchlorylbenzene3-nitro-4-methylperchlorylbenzene 3-amino-4-methylperchlorylbenzene3-bromo-4-Inethylperchlorylbenzene 2,4-dichloro-S-nitroperchlorylbenzene4-thiophenylperchlorylbenzene 4-methoxyperchlorylbenzene 3-B-hydroxynaphthylazo) -perchlorylbenzene2,4-dimethyl-S-sulfoperchlorylbenzene3-sulfonylchlorideperchlorylbenzene In the preparation of the primarycompounds of our invention, perchloryl fluoride and an aromatic compoundcapable of supplying an aryl radical are brought together in thepresence of a Friedel-Crafts catalyst coupling agent in a substantiallynon-alkaline non-aqueous system at temperatures not exceeding 280 C. Thereaction concerned involves the electrophi ic substitution of anaromatic hydrocarbon or a derivative by the perchloryl radical ofperchloryl fluoride. The reaction is categorized as perchlorylation, adescriptive term which is in accordance with the usage set forth by theInternational Union of Pure and Applied Chemistry and approved by theeditors of Chemical Abstracts, a publication of the American ChemicalSociety.

For the preparation of our primary compounds, we prefer to use benzeneor a substituted benzene.

Examples of substituted benzene include toluene; ethyl benzene; thevarious xylenes; mono-, di-, and trihalobenzene; and the variouschlorotoluenes.

The perchloryl fluoride used in practicing our inven tion iscommercially available, but may be prepared by any means known to theart, such as by reacting potassium chlorate with elemental fluorine orby electrolysis of sodium perchlorate in anhydrous hydrofluoric acid, asdescribed in the cited references.

The stoichiometric reaction between perchloryl fluoride and the aromaticcompound involves the use of at least one mole of the former for eachmole of the latter with which it enters into reaction.

The perchloryl fluoride is preferably introduced in gaseous form intothe catalyst-containing mass, but it may be introduced as a liquid, atall times using proper precautions pertaining to the handling ofperchloryl fluoride.

The coupling agents used in carrying out our invention are acidiccompounds of the type known to the art as Friedel-Crafts catalysts.Examples of such coupling agents are AlCl AlBl'g, SbCl Feclg, SnCl BF3and TaCl The preferred coupling agent is A1013. Use of AlCl isespecially preferred because of the ability of the AlCl to convert theHF released in the coupling reaction into a mixture of AlF AlCl and HCl,thus eliminating the problem of having HP in the reactor system. Thecoupling agent is prepared and used in the manner commonly employed inthe utilization of catalysts in Friedel- Crafts types of reactions, aprocedure well known to those working in the art. The Friedel-Craftscatalysts used in the coupling reaction are sensitive to water;therefore, in preferred practice, dry aromatic compounds are employed asreactants, and the reaction system is maintained substantiallyanhydrous. In the preferred manner of practice of the process of thisinvention, using AlCl as coupling agent, it has been found that after HFis liberated from the perchloryl fluoride reactant, and the AlF -AlClmixture forms, the reactivity of the AlCl substantially decreases. Theconsumption of AlCl therefore, is about mole for mole with theperchloryl fluoride and the aromatic compound. With most of theabove-named coupling agents, acceptable results may be obtained whenusing commercial aromatic compounds which normally contain small amountsof water. In such cases, the molar ratio of coupling agent to perchlorylfluoride is at least 1:1 and preferably somewhat greater. The presenceof any large amount of water is undesirable, because of the deleteriouseffect on the catalyst.

In carrying out the coupling reaction, the acidic catalyst used as thecoupling agent is perferably added to the aromatic compound, with thelatter being used alone in excess or dissolved in a solvent, and theperchloryl fluoride is then passed into the mixture, which is preferablyheld at 0 C. to C. by cooling. It is preferred in many instances toemploy as solvent or diluent the same aromatic compound which is beingreacted, it merely being necessary in such cases to make certain thatsaid compound is present in the reaction mixture in substantial excessover the stoichiometric amount required for reaction. This procedure isparticularly applicable when the aromatic reactant is a liquid, such asbenzene, toluene, or a relatively low-melting solid, such asp-dichlorobenzene. When the aromatic compound itself serves as thesolvent, it is used in large excess, and preferably a ratio of from 5 to15 volumes of said compound per volume of catalyst is used.

Alternatively, the perchlorylation reaction can be advantageouslycarried out in the presence of a non-aqueous solvent or diluent whichpreferably is inert to the reactants, such as petroleum ether, diethylether and other lower dialkyl ethers, liquid aliphatic hydrocarbons,e.g., hexane, ligroin, etc. When an added solvent is used, volumessimilar to those above are used, so that the liquid-to-solids volumeratio is preferably from about 5:1 to about 15:1.

As in the case with all chemical reactions, it is good practice tomaintain the reaction mixture at temperatures sufiiciently high to causereaction to proceed at a reasonable rate, but not so high as to causeextensive side reactions and/or decomposition of reactants and product.Temperatures ranging from about l C. to about 280 C. are satisfactory, apreferred range being between 0 C. to 80 C. In many instances thereaction proceeds quite smoothly at ordinary temperatures, such asbetween C. and C., but for most reactions a temperature range of from 0C. to 15 C. is especially preferred.

Pressure is not critical, and the reaction may be conducted atatmospheric pressure, sub-atmospheric pressure, or superatmosphericpressure. Atmospheric pressure is more convenient and is frequentlypreferred.

Agitation of the reaction mixture is beneficial in increasing the rateof reaction.

The perchlorylated product is recovered from the reaction mass byprocedures customarily used in carrying out Friedel-Crafts reactions.See, for example, P. H. Groggins, Unit Processes in Organic Synthesis,4th edition, Chapter XIV, McGraw-Hill Book Company, Inc., N.Y. (1952).

In the preparation of the secondary class of our novel aromaticcompounds, a perchlorylaromatic compound of the primary class is reactedby means of customary reactions applicable to organic compounds in anon-aqueous solution under mildly alkaline, neutral, or acid conditionswith a reactant substance containing a functional group or groups whichis to be introduced either into the nucleus of the perchlorylaromaticcompound or into the substituent group, if one is present, on thearomatic radical. Examples of such reactions are nitration, sulfonation,halogenation, reduction, hydrogenation, amination, cyanation,diazotization, hydrolysis, esterification, oxygenation, couplingcondensation, arylation, etc. In other words our perchlorylated aromaticcompounds are subject to the Whole spectrum of reactions known ingeneral to occur below 280 C. to aromatic compounds under mildlyalkaline, neutral or acid conditions. Procedures useful for transformingour primary perchlorylaromatic compounds into our secondary class ofperchloryl aromatic compounds may be found in most standard textboks andin the chemical literature. Typical of such sources are VartkesMigrdichian, Organic Synthesis, vol. I and II, Reinhold PublishingCorporation, N.Y. (1957); Kirk- Othmer, Encyclopedia of ChemicalTechnology, The Interscience Encyclopedia, Inc., N.Y. (1947, 1957); andRoger Adams et al. Organic Reactions, vol. I-IX, John Wiley & Sons,Inc., N.Y. (19421957).

The

group is highly stable chemically under acid or neutral conditions andis not affected by the reactants used for the introduction of new groupsinto the aromatic nucleus or into its already present substituentgroups. The bond between the aromatic radical and the perchloryl radicalis stable up to about 280 C., around which temperature theperchlorylaromatic compounds decompose explosively. The perchlorylradical is, however, more or less readily replaced by a hydroxy groupupon treatment with an inorganic or organic base under strongly alkalineconditions. Depending upon other substituents present, this replacementmight require anything from less than an hour to a few days of reactiontime at room temperature. The reaction occurs more readily upon heating.Alkaline conditions should therefore usually be avoided except formildly alkaline conditions, i.e., below a pH which is high enough tocause removal of the perchloryl radical, maintained for short periods oftime at moderate temperatures. It has been found, in one unusual caseillustrated by Examples 74 and 75 (disclosed and claimed in copend- 8ing application of Francis L. Scott, Serial No. 841,684, filed September23, 1959), now Patent Number 3,047,- 589 that because of the presence ofa fluoro substituent the perchloryl group Was stable in stronglyalkaline solution held at its boiling point for many hours.

So far as the reactions other than perchlorylation are concerned, e.g.,the chlorinations, other halogenations, nitrations, reductions,diazotizations, acetylations, Sandmeyer recations, hydrolyses,phenylations, couplings, sulfonations, alkylations, haloalkylations, andthe like, procedures known in the art that can be carried out undermildly alkaline, neutral or acid conditions are employed. Theseprocedures include the selection from the known prior art processes ofsuitable solvent media, suitable temperatures and suitable catalysts,where appropriate.

The perchlorylaromatic compounds of our invention are liquids andsolids. Although their general physical and chemical properties aredependent on the organic group of the particular aromatic compoundcoupled with the perchloryl radical of perchloryl fluoride, the presenceof the radical significantly alters the character of the originalorganic compound. For example, benzene, whose boiling point is about C.,reacts with C10 F, B.P. 47.5 C., to form perchlorylbenzene whose boilingpoint is 232 C.

We have found that our novel perchlorylaromatic compounds, for exampleperchlorylbenzene, possess explosive properties. They are thus useful asexplosive charges for blasting and for the manufacture of explosivedevices. They are also useful as high energy fuels. They can be used asintermediates in the preparation of a wide variety of compounds usefulin pharmaceutical and dye applications. They can be used as additivesfor fuels used in internal combustion engines, particularly as cetaneimprovers in diesel fuels.

The following examples, which are by way of illustration and not oflimitation, illustrate the preparation and usefulness of the compoundsof the invention. The parts are by weight unless stated otherwise.

Example 1 133 parts of AlCl are suspended with agitation in about 2600parts of benzene in a vessel in a cooling bath. Perchloryl fluoride gasis passed slowly intothe benzene- AlCl mixture, which is maintained at atemperature of about 40 C. HCl gas is evolved from the reaction mass.Addition of the perchloryl fluoride is stopped when about parts havebeen added and HCl evolution has ceased. The reaction mass is added toabout twice its volume of water. The mass is then steam-distilled. Thebenzene layer thus recovered is evaporated, and the perchlorylbenzenecontained therein, about 70 parts, is recovered as a pale yellow oil.Upon distillation of the oil under high vacuum, about 62 parts ofperchlorylbenzene are recovered as a colorless, oily liquid.Determination of the physical constants of perchlorylbenzene prepared asdescribed above gave the following values: B.P., 232 C.; F.P., 3 C.;refractive index 11 1.5236, and density 30/4 C., 1.185. Analysis of theperchlorylbenzene gave for the formula C H ClO the following values:Calculated: M.W., 160.5: C, 44.90; H, 3.14; Cl, 22.08. Found: M.W., C,44.80; H, 3.26; Cl, 22.27.

The structure of perchlorylbenzene was determined from its infraredspectrum to be The infrared spectrum of perchlorylbenzene showsabsorption between 1670 cm. and 2000 cm. characteristic ofmonosubstituted aromatics. The most striking feature is a very strongband at 1101 cmr' Both perchloryl fluoride and perchloric acid absorbstrongly in this region, at 1312 cm." and 1032 CII'IFI, respectively.This band is assigned to a Cl-O stretching frequency.

The structure of perchlorylbenzene was further confirmed withultraviolet absorption spectrum. Three distinct peaks, characteristic ofbenzene derivatives, were obtained at 255.5, 261.5 and 268.0 me. Themaximum at 261.5 nm is a higher wave length from that of benzene at254.5 mm, characteristic of substituted derivatives of benzene andcomparable to chlorobenzene which shows a maximum at 265 m thusevidencing the C-Cl structure.

Example 2 Meta-xylene, containing AlC1 in suspension, was reacted withperchloryl fluoride in the manner described in Example 1 to form2,4-dirnethylperchlorylbenzene. Reaction to form the perchlorylatedcompound was observed to take place by the evolution of HCl gas andblackening of the AlCl catalyst.

Example 3 Eight parts of anhydrous aluminum chloride were suspended inabout 90 parts of p-xylene and the mixture cooled to 10 C. with anexternal cold water bath. Perchloryl fluoride gas was bubbled throughthe mixture slowly at 10-15 C. HCl gas was evolved and the AlCl catalystbecame a fine black suspension. When evolution of HCl ceased (about 2hours), the reaction mixture was filtered. Steam distillation of thefiltrate, followed by separation and drying of the xylene layer overMgSO and evaporation under vacuum, gave 8 parts of a high boilingliquid. Vacuum distillation gave the pure 2,5-dimethylperchlorylbenzene,a colorless liquid, B.P. 78 C. (p. 2 mm.); M.P. 27-28 C.

Analysis.Calculated for C H ClO C, 50.94; H, 4.81. Found: C, 51.99; H,4.98.

Infrared analysis showed a strong Cl-O band at 1189 cm? comparable toperchlorylbenzene at 1191 cm.1. The spectrum in the 1670-2000 cm.-region indicated a 1,2,5-trisubstituted aromatic ring.

Example 4 Perchloryl fluoride gas was bubbled through a suspension of 13parts of anhydrous aluminum chloride in about 100 parts of fluorobenzeneat 2530 C. HCl gas was evolved. Temperature was maintained by means of awater cooling bath. When evolution of HCl was complete the fine blacksolids were filtered from the fluorobenzene solution before steamdistillation. The organic layer was separated and dried over anhydrousMgSO The fluorobenzene was evaporated under vacuum, leaving a paleyellow oil (12 parts). Vacuum distillation gave the pure4-fluoroperchlorylbenzene, B.P. 53 C./ 0.25 mm. 21 1.5051.

Analysis.Calculated for C H CIFO C, 40.36; H, 2.25; Cl, 19.86. Found: C,40.69; H, 3.28; Cl, 20.32.

Infrared spectrum showed a para-substitution pattern in the 1670-2000cm? region and the strong Cl-O band at 1198 cmr Example Perchlorylfluoride gas was bubbled through a solution of 3 parts of anhydrous AlBrin about 225 parts of benzene at 5 C. for one hour. Five parts ofperchloryl fluoride were used. HBr gas was evolved. The catalyst turnedto a fine black suspension. Dilution of the reaction mass in water andsteam distillation resulted in recovery of perchlorylbenzene. Theproduct was shown by infrared to be identical to the perchlorylbenzeneprepared using A101 as the catalyst.

Example 6 To a solution of 1 part of 3-nitroperchlorylbenzene in about50 parts of ethanol and about 50 parts of concentrated HCl were added 6parts of stannous chloride in small amounts with stirring. The mixturewas heated to 5060 C. and held at that temperature for 20 minutes aftercomplete addition of the stannous chloride. It was then poured over iceand water and neutralized with 10% NaOH solution. The mixture wasextracted three times with diethyl ether. The other extracts werecombined, dried over MgSO and evaporated. S-Aminoperchlorylbenzene wasrecovered in the form of a crude pale yellow liquid. Infrared analysisshowed the Cl-O band and the N-H doublet. The N0 band of the startingnitro compound was eliminated. M.P. 32 C.

Example 7 20 parts of perchlorylbenzene in 80 parts of concentrated H 80were treated with a nitrating mixture consisting of about 25 partsconcentrated H SO and 14 parts of concentrated nitric acid at 20 C. toC. for a period of about one hour. The reaction mass was then pouredover ice. 22 parts of a yellow solid were filtered from the mixture.Upon recrystallization of the solid from a benzene-petroleum ethersolvent a mass of pale yellow needle-shaped crystals were recovered,M.P. 4950 C. The product was identified by analysis as3-nitroperchlorylbenzene. Analysis.Calculated for C H ClNO Cl, 17.25; N,6.81. Found: Cl, 17.27; N, 6.92. The structure of the compound wasdetermined from its infrared spectrum. A very strong absorption bandappears at 1211 cm? and is assigned to the Cl-O stretching frequency.

Absorption at 1350 cm.- and probably 1529 cm.- indicates a nitrosubstituent, while the pattern between 1670-2000 cm.- is characteristicof substitution.

Example 8 Freshly ground AlCl was added to 10 ml. of diethyl ether untilthe ether was saturated. An additional 4 gins. of AlCl and 10 ml. ofbenzene were then added. Perchloryl fluoride was bubbled into themixture at room temperature. The temperature rose to 40 C. and remainedthere during the addition of the perchloryl fluoride. When thetemperature began to fall, indicating the end of the reaction, thereaction mass was steam distilled. Perchlorylbenzene was recovered fromthe distillate as a heavy oil. Its identity was confirmed by infraredanalysis.

The example demonstrates the practicability of the use of an excess ofAlCl in an ether solvent.

Example 9 Using the procedure described in Example 8 technicalnitrobiphenyl was reacted with perchloryl fluoride and excess AlCl atabout 45 C. The reaction was stopped after about 3 hours. The reactionmass was dispersed into ice water. The product was recovered by etherextraction and purified. Infrared analysis confirmed pres ence of theperchloryl group on the nitrobiphenyl structure.

Example 10 Using the procedure described in Example 8 phenol was reactedwith perchloryl fluoride and AlCl at about 40 C. The product formed,4-hydroxyperchlorylbenzene, was shown by infrared to possess theperchloryl group.

Example 11 Anhydrous HCl was passed into a solution of3-aminoperchlorylbenzene in anhydrous ether. A white precipitate formed.The precipitate was recovered by filtration and was washed withanhydrous ether and dried. Vacuum sublimation gave the pure white solidhydrochloride of 3-aminoperchlorylbenzene N EB 01 M. P .decomposes 11Analysis.Ca1culated for C H Cl NO C, 33.98; H, 3.33; N, 6.60. Found: C,32.86; H, 3.96; N, 6.00.

Example 12 The acetyl derivative of 3-aminoperchlorylbenzene wasprepared by treating 3-aminoperchlorylbenzene with ace- ,tic anhydridein acetic acid at 3040 C. and recrystallized from ethanol to give purecolorless needles of (IJlOs NHC 0 CH M. P 136-137 C Analysis.-Calculatedfor C H CINO C, 44.15; H,

3.71; N, 6.44. Found: C, 44.21; H, 3.74; N, 6.55.

Example 13 (a) Perchlorylbenzene in liquid form was subjected to impacton a detonating block. The compound exploded.

12 (b) Perchlorylbenzene was solidified by cooling and was subjected toimpact on a detonating block. Explosion of the compound resulted.

Example 15 Meta-nitroperchlorylbenzene was subjected to impact on adetonating block. The compound exploded.

Example 16 4-nitroperchlorylbenzene is charged into an elongatedbomb-casing equipped with a recessed tube for insertion of a blastingcap. A plurality of such bomb-casings is inserted into bored holes in abed of marble. Upon detonation of the blasting cap's by means of anelectrical det onator, the 4-nitroperchlorylbenzene is exploded andruptures the marble into easily removed sections.

In the following examples are shown additional species of ourperchlorylaromatic compounds and the steps by which they can be made.The step of monoperchlorylation is carried out substantially asdisclosed in Example 1. The steps of chlorination,bromination,iodination, nitration, amination, reduction, diazotization, Sandmeyerreaction, biphenyl synthesis, hydrolysis, etc. are carried out accordingto known procedures.

Exlarrnple Starting Compound Reaction Perchlorylaromatic Product (llloa17 Monochlorobonzene Monoperchlorylation.

O1 ([3103 18 Phenol do Q OH 1 19 Toluene do Q CH;

20 Monochlorination 21 Nitration and reduction.

1 CH3 CH3 C|103 ([1103 N 0g 22 Mononitra'tion *NHZ -NH2 I CH3 CH3 Exlzzmple Starting Compound Reaction Perchlorylaromatie Product 23Monofluotobenzene Monoperchlorylation.

-O1 24 Trichlorlnation F F (I310; (I110:

Ol- Cl 25 Tetrachlorination.

Cl O] OH OH (I110; (IJIOa 26 S ulfonation SO3H OOH 27 AnisoleMOnOperchlorylation.

C! 28 Monochlorobenzene rgoperchlorylanon.

-01 -01 29 Mononitration 30 Displacement of fluorine by thioalkyl group(See Example 74). I F SCH3 I 31 Nitrobiphenyl Moqoperchloryl- NO -QQatxon.

NO NO 32 Mononitration c1 -c1 z 33 Reduction N03 NH;

Exlazmple Starting Compound Reaction 'Per'chldrylaromatic Product ([3103([llOa 1 CI 34 Mononitratlon as acetyl derivative. NH NHg- -NO;

CH: 35 Toluene Monoperchlorylation.

OH Cl- CH; 36 Trlchlorination -CH3 I! 37 Trichlorination 1 C1 C1 38Perchlorination.

Br 39 Monoperchlorylation.

CH; 40 MOQODBIOIIIOIYI- anon.

-CH; CH 41 N itration, reduction, diazotiza- CH tion, Sandmeyer CH3- -CNreaction.

F 42 Monoperchlorylation.

-F F 43 Dich1orinati0n..... v

F- F Cl I Cl Exlsarmple Starting Compound Reaction PerchlorylaromaticProduct F O] F 44 Dichlorination (fgHi C103 O H 45 Monoperchlorylation.

46 Nitration, reduction, diazotiza- 01 tion and hy- OH C1 drolysis.

O1 1 (iJlOa (3103 47 Nitration, reduction, diazotization and biphen- O1yl synthesis.

01 01 Elk (I310:

Br 48 Monoperchlorylation.

Br (1110a $103 Ol 49 Dichlorination Cl Br I Br Br (13H; (IJIOa -OH: 50Monoperch1ory1- ation. CH3

CH3 ([3103 (I303 -CH 011 01 51 Chlorination of methyl radicals.

CH3 CHgCl CH CH3 52 Moqoperchlorylmu. CH3- CH 01 (IIH (1310a CH3 53Monoperchlorylation. CH3 CH CH CH Exlz Imple Starting Compound ReactionPerchlorylaromatic Product CH3 CH: 54 Mononitration CH3 CH3 NO,

I CH3 CH3 C1 55 Monoperchlorylation. g1 01 -01 56 Nitration, reduction,diazotiza- C1 C1 tion and iodina- 1 C1 tion. I 31 01 O1 57Monoperehlorylation. 01 01 F O1 O1 G1 58 Dichlorination CH; C|105 CH3CH3 59 Monoperchloryl- I ation. CH3 --CH3 CH3- CH3 CH3- CH3 60Nitration, reduction, dizaotization and iodina- I I ti0n CH CH3 OH: C113-CH3 51 Monoperchlorylation. CH3 CH3 CH3 CH3 CH3 CH:', CH: 62 Nitrationand reduction.

CH3 -CH3 CH3 -CH3 C1 63 Monoperchlorylation.

Exlarmple Starting Compound Reaction Perchlorylaromatic Product Nitration, reduc- 64 tion, diazotization, and coupling with N:IIT

OH OH- tlllos (710 N03 65 Mononitration NHCOOH NHOOOH;

NH2 5 Nitration, reduction, second Ol nitration and NH Cl reduction.(3103 03 (1102 7 Nltration, reduction, diazotization and decompositionof the diazonium compound formed. (1110 C110; C103 68 Nitration,reduction.

69 Controlled reduction. -NO2 O|l03 (F G|1O 70 Controlled reduction. oNHNH 71 Oh1oromethylation I CHzCl Example 72 is purified byrecrystallization from chloroform, M.P. zoo-201 Analysis.-Calc. for C HClN O C, 58.10; H, 3.35. Found: C, 57.34; H, 3.45.

Infrared absorption gives a maximum at 464 my, orange region of thevisible spectrum.

Other nitrogen-containing derivatives of perchlorylaromatic compoundscan be prepared by amination of a perchlorylaromatic compound, e.g.,perchlorylbenzene, followed by substitution of the hydrogen atoms of theamine group to form acetamido-, hydrazino-, triazolyl-, phenylazo-, ornaphthylazoperchloryl-aromatic compound, using known procedural methodsfor carrying out each of said synthesis steps.

Example 73 A piece of wool cloth is thoroughly Wetted with hot Water andis immersed in a dye bath held at F. and containing 1.0% of3-(B-hydroxynaphthylazo)-perchloryl-benzene, 20% Glaubers salt crystalsand 5% of 28% acetic acid. All weights are based on the Weight of thedry cloth. The temperature is raised rapidly to boiling in about 15minutes and the boiling is continued for 1 hour. 1.0% of sulfuric acidis then added and boiling continued for another 30 minutes. The woolcloth is rinsed in water, extracted and dried. A deep orange color isthus imparted to the cloth. The cloth withstands prolonged exposure insunlight without appreciable loss of color by fading.

Similarly, dyes may be made from any of the perchlorylaromatic compoundsof this invention. If the compound does not already contain an aminogroup such a group is introduced by nitration and reduction inaccordance with Examples 6 and 7. The perchlorylaromatic amine is thendiazotized and the perchlorylaromatic diazonium compound reacted with asuitable auxochrome compound, i.e., one containing OH, NH OCH a 3)2 6 5N(CH3)C6H5, NH-SO 'C H NH-OH or, NH-NH to furnish a dye, as described inExample 72.

Example 74 4-fiuoroperchlorylbenzene (4.0 g., 0.0233 mole) and about 200ml. of sodium methoxide in methanol (0.221 mole) are refluxed together.Reaction is substantially complete in about 90 minutes. The cooledreaction mixture is diluted with water and extracted with ether. Theether extract is dried over anhydrous magnesium sulfate, filtered, andevaporated to recover the product, 4-methoxyperchlorylbenzene, an oilyliquid, 11 1.5307. Infrared spectrum confirms presence of the perchloryland methoxide groups.

Example 75 A mixture of 4 g. of 4-fiuoroperchlorylbenzene (0.0233 mole),2.45 g. of thiophenol (0.0233 mole) and about 100 ml. of 0.221 molarsodium methoxide in methanol are refluxed for 18 hours. The cooledreaction mixture is diluted with water and extracted with ether. Theether extract is dried over anhydrous magnesium sulfate, filtered, andthe ether evaporated. The product, 4-thiophenylperchlorylbenzene, is anoily liquid, r1 1.5778. Infrared spectrum confirms presence of theperchloryl and thiophenyl groups.

Example 76 Perchlorylbenzene is dissolved in an excess oftetrachloroethane. About 1% of anhydrous FeCl;,, based on the weight ofperchlorylbenzene, is added to the solution as a catalyst. Gaseouschlorine is added to the solution With stirring, and cooling of thereaction vessel, maintaining a temperature of about C. to C. When about60% of the theoretically required amount of chlorine has been added, thechlorination is stopped, to avoid over-chlorination of the4-chloroperchlorylbenzene product. A small amount of3,4-dichloroperchlorylbenzene is formed as by-product. The4-chloroperchlorylbenzene is recovered from the solvent as an oilyliquid.

Other nuclearly chlorinated compounds can be similarly prepared bycontinuing the chlorination at a temperature below 280 C. to substituteup to 5 atoms of chlorine into the perchlorylbenzene ring. In this way,tri-, tetra-, and pentachloroperchlorylbenzenes can be obtained. Othercatalysts may also be used, e.g., metallic iron, iodine,aluminum-mercury couple, and antimony monochloride. Bromoandiodoperchlorylbenzene compounds can similarly be prepared, using theappropriate halide catalyst, e.g., FeBr or I or metallic iron.

Example 77 Homologs of perchlorylbenzene can be nuclearly halogenated inthe same manner as perchlorylbenzene in Example 76 to formalkylhaloperchlorylaryl compounds. Perchloroylxylene, e.g.,2,4-dimethylperchlorylbenzene is progressively chlorinated, first at 5l0C. and then by raising the temperature gradually to about 60 C.,

24 with gaseous chlorine in the presence of ferric chloride catalystin asuitable solvent, preferably tetrachloroethane, or in C Cl nitrobenzene,ether, alcohol, CHCl or glacial acetic acid, to form3-chloro-2,4-dimethylperchlorylbenzene,3,5-dichloro-2,*4-dimethylperchlorylbenzene, and 2,4-dimethyl-3,5,6-trichloroperchlorylbenzene.

The corresponding bromo-2,4-dimethylperchlorylbenzenes are similarlyformed from Br using ferric bromide catalyst.

Example 78 Haloalkylperchlorylbenzene compounds are prepared bysubstitution of hydrogen atoms in the side chain of analkylperchlorylbenzene compound, e.g., 2,4-dimethylperchlorylbenzene,with a halogen at higher temperatures than used in Examples 76 and 77 orby illumination of the reaction mass in the absence of catalysts.

Chlorination of 2,4-dimethylperchlorylbenzene is carried out in a glasstower packed with glass rings and illuminated with mercury lamps(ultra-violet light). The lamps are spaced about 4 feet apart.2,4-dimethylperchlorylbenzene is heated to 65 C. to 75 C. and is fedinto the top of the tower at a uniform rate. Dry chlorine gas is passedup the tower. The temperature of the tower is maintained just below thereflux point. 2,4-chloromethylperchlorylbenzene is recovered as theproduct.

The corresponding 2,4-bromomethyland 2,4-iodomethylperchlorylbenzenesare similarly prepared by using Br and I respectively in place of the C1Example 79 Perchlorylbenzene and its homologs, particularly the highlyalkylated derivatives and those containing hydroxyl groups in thenucleus, can be chloromethylated by reacting the perchlorylaryl compoundwith formaldehyde and hydrochloric acid at a temperature below 280 C.Sulfuric acid, the chlorides of zinc, aluminum or tin are effectivecatalysts, although with the higher alkylated perchlorylaromaticcompounds, e.g., 2,4,5-trimethylperchlorylbenzene, a catalyst isunnecessary. Thus, 3- perchlorylbenzyl chloride is readily obtained byreacting perchlorylbenzene with formaldehyde and dry halogen chloride inthe presence of sulfuric acid at room temperature.

The corresponding 3-perchlorylbenzyl bromide and -iodide are similarlyprepared by using dry HBr and HI in place of the dry HCl.

Example 80 Perchlorylbenzene and its homologs are readily sulfonatedwith concentrated sulfuric acid by heating a mixture of theperchlorylaryl compound with the acid at a sufliciently high temperaturebelow 280 C. Thus, perchlorylxylenesulfonic acid, i.e.,2,4-dimethyl-5-sulfoperchlorylbenzene, is obtained by adding2,4-dimethylperchlorylbenzene to about the theoretically required weightof' about 100% sulfuric acid and heating the mixture at about 80 C. C.until the 2,4-dimethylperchlorylbenzene is dissolved.

Example 81 The diazotized derivatives of aminoperchlorylbenzene and itshomologs are readily obtained by reacting aminoperchlorylaromaticcompounds with nitrous acid, or ma terials forming nitrous acid insolution in concentrated mineral acid, such as H 80 HCl, HBr, attemperature below 280 C. Thus, 3 perchlorylbenzenediazonium chloride isobtained by diazotizing 3-aminoperchlorylbenzene with sodium nitrite inconcentrated HCl at about 0" C.

Many different embodiments of this invention may be made withoutdeparting from the scope and spirit of 26 wherein Q is a radicalselected from the group consisting of -'NH --NO NH-HC1, -NHCOCH and c isan integer from 1 to 2.

2. 3-nitrope-rchlorylbenzene. 3. 3-aminoperchlorylbenzene. 4.S-aminoperchlorylbenzene hydrochloride. 5. 3-acetamidoperchlorylbenzene.

No references cited.

UNITED STATES PATENT OFFICE CERTIFICATE OF (IQRRECTIGN Patent No, 3, ll270 l July 28 1964 Charles E. Inman et all,

It is hereby certified that error appears in the above numbered pat antrequiring correction and that the said Letters Patent should read ascorrected below Column 8, line 9 for "recations" read reactions line28,, for "C10 F" read C10 5 columns 15 and 16 in the table under theheading "Perchlorylaromatic Product and opposite "Example No. 41" theformula should appear as shown below instead of as in the patent:

CH (ZN column 26 lines 3 to 10 the left-hand formula shouldappear asshown below instead of as in the patent:

Signed and sealed this 17th day of November 1,9640

(SEAL) Attest:

ERNEST W, SWIDER EDWARD J, BRENNER Attesting Officer Commissioner ofPatents UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PatentNo., 3, l42 704 July 28 1964 Charles E, Inman et ale It is herebycertified that error appears in the above numbered patent requiringcorrection and that the said Letters Patent should read as correctedbelow.

Column 8, line 9 for "recations" read reactions line 28 for "C10 F" read(210 columns 15 and 16 in the table under the heading"Perchlorylaromatic Product" and opposite "Example N0. ll" the formulashould appear as shown below instead of as in the patent:

CH I QN column 26 lines 3 to 10 the left-hand formula shouldappear asshown below instead of as in the patent:

Signed and sealed this 17th day of November 1964,

(SEAL) Attest:

ERNEST W, SWIDER EDWARD J, BRENNER Attesting Officer Commissioner ofPatents

1. NITROGEN-CONTAINING PERCHLORYLAROMATIC COMPOUNDS HAVING THE FORMULA